Bulk single crystal gallium nitride and method of making same

ABSTRACT

A single crystal M*N article, which may be made by a process including the steps of: providing a substrate of material having a crystalline surface which is epitaxially compatible with M*N; depositing a layer of single crystal M*N over the surface of the substrate; and removing the substrate from the layer of single crystal M*N, e.g., with an etching agent which is applied to the substrate to remove same, to yield the layer of single crystal M*N as said single crystal M*N article. The bulk single crystal M*N article is suitable for use as a substrate for the fabrication of microelectronic structures thereon, to produce microelectronic devices comprising bulk single crystal M*N substrates, or precursor structures thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of U.S. patent application Ser. No. 09/929,789filed Aug. 14, 2001 in the names of Michael A. Tischler, Thomas F. Kuechand Robert P. Vaudo for “Bulk Single Crystal Gallium Nitrate and Methodof Making Same,” issued Dec. 6, 2005 as U.S. Pat. No. 6,972,051, whichin turn is a continuation of U.S. patent application Ser. No.08/955,168, filed Oct. 21, 1997 in the names of Michael A. Tischler,Thomas F. Kuech and Robert P. Vaudo for “Bulk Single Crystal GalliumNitrate and Method of Making Same,” now abandoned, which in turn is acontinuation-in-part of U.S. patent application Ser. No. 08/188,469filed Jan. 27, 1994 in the names of Michael A. Tischler, and Thomas F.Kuech for “Method of Making a Single Crystal Ga*N Article,” issued Oct.21, 1997 as U.S. Pat. No. 5,679,152.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to bulk single crystal binary, ternary orquaternary metal nitrides such as gallium nitride, such metal nitridesbeing referred to broadly hereafter by the symbol M*N, including singlecrystal M*N substrate articles useful for formation of microelectronicstructures thereon, as well as to an appertaining method of forming M*Nin single crystal bulk form.

2. Description of the Related Art

The III-V nitrides, in consequence of their electronic and opticalproperties and heterostructure character, are highly advantageous in thefabrication of a wide range of microelectronic structures. In additionto their wide band gaps, the III-V nitrides also have direct band gapsand are able to form alloys which permit fabrication of welllattice-matched heterostructures. Consequently, devices made from theIII-V nitrides can operate at high temperatures, with high powercapabilities, and can efficiently emit light in the blue and ultravioletregions of the electromagnetic spectrum. Devices fabricated from III-Vnitrides have applications in full color displays, super-luminescentlight-emitting diodes (LEDs), high density optical storage systems,excitation sources for spectroscopic analysis applications, etc. Hightemperature applications are found in automotive and aeronauticalelectronics.

To effectively utilize the aforementioned advantages of the III-Vnitrides, however, requires that such materials have device quality anda structure accommodating abrupt heterostructure interfaces, viz., III-Vnitrides must be of single crystal character, substantially free ofdefects that are electrically or optically active.

A particularly advantageous III-V nitride is GaN. This nitride speciescan be utilized in combination with aluminum nitride (AlN) to provideoptically efficient, high temperature, wide band gap heterostructuresemiconductor systems having a convenient, closely matchedheterostructure character similar to that of GaAs/AlAs. Indium nitridemay also be added to GaN or AlN to provide additional advantages.

Corresponding advantages are inherent in ternary GaN compositions of theshorthand formula MGaN, wherein M is a metal compatible with Ga and N inthe composition MGaN, and the composition MGaN is stable at standardtemperature and pressure (25° C. and 1 atmosphere pressure) conditions.Examples of potential M species include Al and In. Such compounds havecompositions described by the formula M_(1-x)Ga_(x)N, where x rangesfrom 0 to 1. The addition of a third compatible metal providesquaternary alloys of general formula M_(1-x-y)M′_(y)Ga_(x)N, where M andM′ are compatible metals, in particular Al and In, and x and y rangefrom 0 to 1. Such quaternary alloys are referred to by shorthand formulaAlGaInN.

Alloys of GaN, AlN or InN with silicon carbide (SiC) may be advantageousbecause they can provide modulated band gaps. Such alloys have in thepast been difficult to grow in single crystal form.

For ease of reference in the ensuing disclosure, therefore, the term“M*N” is defined as including binary (e.g., GaN), ternary (MGaN), andquaternary (MM′GaN) type gallium nitride type compounds, as well as SiC,SiC/AlN alloys, SiC/GaN alloys, SiCInN alloys, and other relatedcompounds such as alloys of SiC with AlGaN. All possible crystal formsare meant to be included in this shorthand term, including all cubic,hexagonal and rhombohedral modifications and all SiC polytypes. Examplesof these compounds include AlN, InN, AlInN, AlGaN, InGaN, and AlInGaN.

For device applications, therefore, it would be highly advantageous toprovide substrates of M*N, for epitaxial growth thereon of any of theM*N materials, especially GaN, AlGaN, InGaN, or SiC, for the productionof heteroepitaxial devices. Unfortunately, however, it heretofore hasnot been possible to produce GaN in single crystal bulk form, and forall M*N materials, growth of high quality bulk single crystals has beenfraught with difficulty.

It therefore would be a significant advance in the microelectronics art,and is correspondingly an object of the present invention, to provideM*N in bulk single crystal form, suitable for use thereof as a substratebody for the fabrication of microelectronic structures.

It is another object of the present invention to provide an appertainingmethod for the formation of bulk single crystal M*N which is relativelysimple and may be readily achieved using conventional crystal growthtechniques in an economic manner.

Other objects and advantages of the invention will be more fullyapparent from the ensuing disclosure and appended claims.

SUMMARY OF THE INVENTION

In one aspect, the present invention relates to a method of making asingle crystal M*N article, including the steps of:

-   -   1. providing a substrate of material having a crystalline        surface which is epitaxially compatible with M*N under the        conditions of M*N growth;    -   2. depositing a layer of single crystal M*N over the surface of        the substrate; and    -   3. etchably removing the substrate from the layer of single        crystal M*N to yield the layer of single crystal M*N as said        single crystal M*N article.

A key point of this invention is that the sacrificial substrate isetched away in situ, while the substrate/M*N structure is preferably ator near the growth temperature.

The sacrificial substrate may for example include a crystallinesubstrate material such as silicon, silicon carbide, gallium arsenide,sapphire, spinel (MgAl₂O₄), MgO, ScAlMgO₄, LiAlO₂, LiGaO₂, ZnO, or anon-crystalline substrate of a material such as graphite, glass, M*N,SiO₂, etc., for which a suitable etchant may be employed to remove thesacrificial substrate by etching. In the case of silicon and galliumarsenide, for example, HCl gas may be usefully employed. Additionalsubstrates include silicon-on-insulator (SOI) substrates, compliantsubstrates of the type disclosed in U.S. Pat. No. 5,563,428 to B. A. Eket al., and substrates containing buried implant species, such ashydrogen and/or oxygen. As a further alternative for the sacrificialsubstrate on which the M*N is grown, twist-bonded substrate structuresmay be used, i.e., where the substrate of crystalline material is bondedto another single crystal substrate material with a finite angularcrystallographic misalignment. As yet another alternative, the substrateof crystalline material may be bonded to a suitable material, whichpreferably can be easily removed or has a similar thermal coefficient ofexpansion as the M*N.

The layer of single crystal M*N may be deposited directly on the surfaceof the crystalline or non-crystalline substrate, or alternatively it maybe deposited on an uppermost surface of one or more intermediate layerswhich in turn are deposited on the crystalline substrate. The one ormore intermediate layers may serve as a buffer layer to enhance thecrystallinity or other characteristics of the M*N layer, as a templatefor the subsequent M*N growth thereon, or the intermediate layer(s) mayserve as protective layer(s), or as an etch stop to prevent the etchantfor the sacrificial substrate from etching into the M*N material.

When the substrate material has a protective layer or template layerdeposited thereon, such layer is deposited on the substrate prior togrowth of the M*N layer on the substrate, but such layer, or otherintermediate layer(s), may be formed in situ in the growth chamber priorto initiation of growth of M*N thereon.

The growth of the M*N material may be carried out in a hydride vaporphase epitaxy (HVPE) reactor. As mentioned, a protective layer may beemployed to prevent decomposition of the single crystal substratesurface while M*N growth is proceeding. Such protective layer should beof a material favorable for M*N deposition. Examples include materialssuch as M*N and alloys thereof, wherein the protective layer is of adifferent material than the main body of the substrate, or is otherwisedifferently formed on the main body of the substrate, e.g., underdifferent process conditions. The protective layer may be formed by anysuitable technique such as for example sputtering, chemical vapordeposition, molecular beam epitaxy (MBE), vapor phase epitaxy (VPE),etc.

In another aspect, the invention utilizes the outdiffusion of specificspecies from the substrate into the M*N layer to provide enhancedproperties of the final M*N product. An example of this aspect is thegrowth of M*N on a silicon substrate. In this case, Si can be caused todiffuse out of the silicon substrate and into the M*N. This diffusionwill form a thin M*N region which is heavily doped with silicon.Silicon-doped M*N is n-type, and this structure is advantageous incertain device structures, as for example for making ohmic contacts tothe back surface of the M*N layer or for forming p-n junctions.

In another aspect, the invention may be carried out with a substratewhich has been implanted with hydrogen, whereby during the deposition ofM*N or thereafter (during an elevated temperature exposure separationstep) hydrogen builds pressure in situ in the heated substrate which inturn effects fracture of the substrate from the M*N material, to yieldthe M*N product article.

In another aspect, the invention relates to bulk single crystal M*Narticles, such as are suitable for use as substrates for the fabricationof microelectronic structures thereon. As used herein, the term “bulksingle crystal M*N” refers to a body of single polytype crystalline M*Nhaving three dimensional (x,y,z) character wherein each of thedimensions x, y is at least 100 micrometers and the direction z is atleast 1 μm. In the preferred practice of the invention, the singlecrystal M*N product will be of cylindrical or disc-shaped form, withdiameter d and thickness z, where d is at least 100 μm and z is at least1 μm. In a preferred aspect, each of the dimensions d and z is at least200 micrometers. The bulk single crystal M*N article may most preferablyhave a thickness dimension z of at least 100 micrometers, and diameterdimension which is at least 2.5 centimeters.

Other aspects, features and embodiments of the invention will be morefully apparent from the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a bulk single crystal M*N articleaccording to one aspect of the invention.

FIG. 2 is a side elevation view of a silicon substrate useful as asupporting base for deposition of single crystal M*N thereon.

FIG. 3 is a side elevation view of the silicon substrate of FIG. 2,having a layer of single crystal M*N deposited thereon.

FIG. 4 is a side elevation view of the silicon/M*N structure of FIG. 3,showing the etching action of a silicon etchant on the silicon substrateportion of the structure.

FIG. 5 is a side elevation view of the silicon substrate of FIG. 2,having an intermediate layer of silicon-doped n-type M*N thereon, withan upper layer of single crystal M*N deposited on the top surface of theintermediate layer of silicon-doped n-type M*N.

FIG. 6 is a side elevation view of the article of FIG. 5 after removalof the substrate portion thereof, yielding a product article comprisinga layer of single crystal M*N having associated therewith a bottomsurface layer of silicon-doped n-type M*N.

FIG. 7 is a schematic depiction of a light emitting diode devicefabricated on a single crystal M*N article according to one aspect ofthe invention.

FIG. 8 is a schematic depiction of an ohmic contact structure fabricatedon a single crystal M*N article according to one aspect of theinvention.

FIG. 9 is a schematic of a wafer carrier suitable for carrying out theprocess of the present invention, showing (a) the sacrificial substrateat the start of the M*N growth, (b) a M*N layer grown on the sacrificialsubstrate, and (c) the M*N substrate after removal of the sacrificialsubstrate.

DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF

The present invention is based on the discovery that single crystal M*Narticles of a self-supporting structural character can be readily formedby the deposition of single crystal M*N on a substrate epitaxiallycompatible with the single crystal M*N, followed by in-situ removal ofthe sacrificial substrate at the growth temperature. The substrate isremoved by etching it away from the single crystal M*N, at the M*Ngrowth temperature or at a temperature in proximity to the growthtemperature, to yield the single crystal M*N as a product article.

Since no M*N substrates currently (before the making of the presentinvention) exist, growth of these compounds must initially take placeheteroepitaxially, for example GaN on silicon. Two types of defectsarise as a result of heteroepitaxial growth. The first is dislocationsdue to the lattice mismatch between the M*N layer and the substrate. Thetypical substrate for GaN is sapphire, which has a 13.8% latticemismatch to GaN. SiC is a closer lattice match (≈3%), but the mismatchis still quite large. Many other substrates have been used, but all ofthem have large lattice mismatches and result in a high density ofdefects in the grown layers.

The second kind of defect is dislocations generated during cool-downafter growth as a result of different thermal coefficients of expansionof the substrate and epitaxial layer. In accordance with the presentinvention, a method for reducing or eliminating the generation of thesedefects is employed to produce large area, high quality single crystalM*N substrates.

In carrying out the present invention, a sacrificial substrate isemployed, upon which is nucleated the M*N layer. The M*N layer is grownon the substrate to the desired thickness and then the substrate isetched away, in-situ, at temperatures close to the growth temperature.Suitable temperatures for the etching step (close to the growthtemperature) are desirably within 300° C., and preferably within 100°C., more preferably within 50° C., and most preferably within 25° C. ofthe temperature at which the M*N layer is grown.

Dislocations arising from the lattice mismatch are reduced in density bygrowing thick M*N layers. It is known that the misfit dislocationdensity decreases with epitaxial layer thickness, and in the practice ofthe present invention, very thick (25-1000 μm) layers can be grown. Infact, if the sacrificial substrate is more easily deformable than M*Nand is very thin (extremely thin silicon substrates are commerciallyavailable, in thicknesses as thin as 2-5 μm), growth of a thickoverlayer of M*N may have the effect of pushing the defects into thesacrificial substrate, leaving a substantially defect-free M*N singlecrystal product after the etching step. The misfit dislocation densitycan be further reduced by using buffer layers which may be a singlecompound layer, a compositionally graded layer structure, or asuperlattice structure comprising alternating layers A and B, where Aand B are selected from GaN, AlN and InN and alloys of SiC with thesenitrides. In general, the strained superlattice can comprise from 5 to200 alternating A,B monolayers. By using such superlattices, it ispossible to force misfit dislocations to the edge of the substrateinstead of permitting them to propagate up into the growing layer. Suchsuperlattice buffer layers have been characterized previously (Tischleret al., Applied Physics Letters, 46, p. 294 (1985)).

Dislocations due to the different thermal coefficients of expansion areeliminated in the practice of the present invention by in-situ removalof the substrate at or near the growth temperature. The in-situ removalmay be effected by the introduction of halogenated gaseous species (i.e.HCl, HF, etc.) which will etchably remove the sacrificial substrate attemperatures close to the growth temperature.

In one implementation, the M*N growth process may be performed in a twochamber system with the sacrificial substrate separating the twochambers of the system. By way of example, the two chambers may beseparated by a carrier member having holes or openings in it which arethe same size as the sacrificial substrate. Small tabs or otherretention structures may be used on the bottom of the carrier member tohold the substrate in place. The M*N precursors are introduced in onechamber to cause the deposition of the M*N layer. The growth of the M*Nlayer proceeds both perpendicular as well as parallel to the substratesurface. After several hundred microns of growth, the M*N will extendover the edge of the sacrificial substrate. This overhang may assist inproviding a suitable seal between the two chambers. Sealing is furtherenhanced during the growth process by keeping the pressures in the twochambers substantially equal or slightly lower in the depositionchamber, to minimize diffusion. During or after the growth of the M*Nlayer and preferably without reducing the temperature, the gaseousetching species are introduced in the other chamber to etchably removethe sacrificial substrate.

Alternatively, an etchant may be chosen which preferentially etches thesacrificial substrate or the M*N layer may be grown to a much greaterthickness than the thickness of the sacrificial substrate, so that uponetching, the single crystal M*N product remains. An intermediate etchstop layer may be initially formed on the sacrificial substrate, toprevent the etchant from effecting removal of material other than thesacrificial substrate material.

In one version of this process, the M*N layer is deposited and then thesubstrate is etchably removed. In another embodiment of this process,M*N deposition and substrate removal are performed simultaneously.

As a result, the sacrificial substrate is removed, leaving the M*N layersitting in the recess of the carrier member. During the etchingsequence, cross-diffusion may be minimized by keeping the pressure inthe growth chamber equal to or slightly higher than the pressure in theetching chamber. Finally, the carrier member may be withdrawn to unloadthe two-chamber system.

It is apparent from the foregoing that such two-chamber system, or otherapparatus system for carrying out the present invention, can be scaledup to grow M*N layers on many sacrificial substrates concurrently.

In another embodiment of this process, the growth takes place in amulti-reactor system where first one side of the substrate is exposed tothe gas species used for deposition of the desired material. Then thesubstrate or substrates are transferred to a different chamber where theother side of the substrate is exposed to gas species to etch off theoriginal substrate material.

As another process variation, a substrate which has been implanted withhydrogen, e.g., by ion implantation thereof, may be used for the growthof M*N. During the deposition of M*N or thereafter during an elevatedtemperature exposure separation step, the implanted hydrogen buildspressure in situ in the heated substrate to cause fracture of thesubstrate from the M*N material, thereby yielding the M*N productarticle.

Depending on the desired goals of the growth process, growth of M*N cantake place in either the kinetically limited regime or the masstransport limited regime. If growth occurs in a kinetically limitedregime, this would permit stacking of the substrates in a furnace forsimultaneous uniform M*N deposition on a large number of substrates. Inanother embodiment, growth could take place in the mass transportlimited regime, which would maximize the growth rate and lead to shortthroughput times.

In a specific embodiment, the sacrificial substrate is silicon and thesubstrate to be produced is GaN. Growth begins by heating the silicon tothe growth temperature (in the range of 800-1300° C.) and introducingthe growth precursors for GaN formation. In one preferred method, thisgrowth process involves initial growth of a silicon buffer layer on thesilicon substrate to provide a clean nucleation layer for subsequentgrowth. The supply (flow) of the silicon precursors is then turned off,and the supply (flow) of the GaN precursors is turned on. The GaN layeris grown to the desired thickness (1-1000 μm, preferably 100-300 μm) andthe supply (flow) of the GaN precursors is turned off. The etchingspecies is then introduced (for example HCl) and the silicon substrateis etchably removed. Silicon can be etched using HCl over a wide rangeof temperatures (700-1200° C.). Typical GaN growth temperatures areabout 1000-1100° C., and so a temperature regime may be selected that issuitable for both growth and etching. The etching time can be reduced byusing pre-thinned sacrificial substrates. The remaining GaN layer isthen cooled and removed from the reactor.

The growth of GaN layers or films by vapor phase processes is well-knownin the art. GaN may be grown using trimethylgallium and ammoniaprecursors. This process produces high quality material, but theprecursors are expensive and the GaN growth is usually done in acold-wall reactor, which may complicate heating of the substrate duringthe etching step. Alternatively, GaN may be grown by a chemical vaportransport method, in which gallium and ammonia are the source materials,and a stream of HCl is passed over the gallium to transport it into thereactor in the form of gallium chloride. This method has the advantagethat the sources are somewhat more economical and the process isnormally carried out in a hot wall reactor.

It will be understood from the foregoing that in addition to GaN, otherM*N species can be grown in a similar fashion. In fact, M*N ternary orquaternary species of precisely specified or of graded composition canbe easily produced because the composition is controlled by the gasphase composition during growth. Controlling composition by controllingthe ratio of gas phase reactants is much easier than composition controlwhen growth occurs from a liquid melt. Substrates with variations indopant concentration or in dopant type can also be easily produced.Other materials besides the III-V nitrides could also be grown in thisfashion, for example silicon carbide. Some suitable sacrificialsubstrates for this process include silicon, GaAs and InP.

It is possible that the constituents of the sacrificial substrate mayact as a dopant for the desired substrate layer, either by a solid statediffusion process through the interface between the sacrificialsubstrate and into the M*N layer or by “auto-doping,” wherein the someamount of the sacrificial substrate material enters the vapor phase atthe growth temperature and dopes the M*N layer as it is growing. If thislatter situation is the case, the back side of the sacrificial substratecould be covered with a suitable mask such as silicon dioxide or siliconnitride to prevent autodoping of the grown layer. However, there may besome diffusion of the sacrificial substrate material into the desiredgrown layer at the interface. This could be beneficial, as for examplein the case of a sacrificial silicon substrate and a grown GaN layer, inwhich the silicon would form a heavily doped n-type layer at the back ofthe substrate. Such heavily doped n-type layer would be advantageous forforming n-type ohmic contacts. If this layer were not desired, it couldbe etched or polished off after the growth process had been completed.

The advantages of the method of the present invention are:

-   -   1. Large diameter substrates can be produced. The limit is the        available size of the sacrificial substrate. For example if the        sacrificial substrate is silicon, this could produce substrates        greater than 10 inches in diameter.    -   2. The substrates are essentially ready for subsequent        processing after growth. No orienting, coring, flatting, or        sawing are required as in bulk growth. Some minor polishing may        be required.    -   3. Many substrates can be produced simultaneously.    -   4. No defects from thermal coefficient of expansion differences        are produced.    -   5. The defect density can be further reduced by using buffer        layers such as a strained layer superlattice.    -   6. Heavily doped back contact layers for ohmic contacts may be        produced.    -   7. Substrates of varying compositions can be easily produced.        For example ternary substrates with pre-selected stoichiometries        can be produced easily because the product composition is        controlled by the gas phase composition. Such gas phase ratio        control is much easier than composition control when growth        occurs from a liquid melt. Substrates with compositional        variations can also be easily produced, because the gas phase        ratio can be varied during growth.    -   8. The doping density in the substrates can be easily        controlled, again by gas phase composition control. No problems        associated with segregation coefficient issues are involved. In        addition, the doping in the substrate can be varied, if desired,        throughout the thickness of the single crystal M*N substrate        being prepared.    -   9. In a potential embodiment, a single crystal M*N substrate and        a device structure could be grown in one cycle.

The sacrificial substrate epitaxially compatible with the single crystalM*N may be any suitable crystalline material, on which M*N may bedeposited by suitable techniques, such as vapor deposition techniques,including chemical vapor deposition (CVD), chemical vapor transport(CVT), physical vapor deposition (PVD), plasma-assisted CVD, etc.Specific examples include sacrificial substrates of silicon, siliconcarbide, gallium arsenide, spinel (MgAl₂O₄), MgO, ScAlMgO₄, LiAlO₂,LiGaO₂, ZnO, sapphire, etc., with silicon and silicon carbide being mostpreferred. Alternative substrates include silicon-on-insulator (SOI)substrates, compliant substrates of the type disclosed in U.S. Pat. No.5,563,428 to B. A. Ek et al., and substrates containing buried implantspecies, such as hydrogen and/or oxygen. The sacrificial substrate, onwhich the M*N is grown, may also comprise a twist-bonded substrate.Non-crystalline materials are potentially useful, e.g., graphite, glass,M*N, SiO₂, etc. The substrate may be bonded to a suitable material,which preferably can be easily removed or has a similar thermalcoefficient of expansion as the M*N.

While it is typically preferred in the practice of the invention toconduct the etch removal of the sacrificial substrate at a temperaturein the close vicinity of the growth temperature (e.g., within 100° C. ofthe growth temperature), it is possible within the broad scope of theinvention to perform the etch removal of the sacrificial substrate fromthe M*N substrate at a temperature of more than 100° C. above the growthtemperature of the M*N material, or alternatively at a temperature ofmore than 100° C. below the growth temperature of the M*N material.Generally, the etch removal of the sacrificial substrate should becarried out a temperature within 300° C. of the growth temperature.

As mentioned, the M*N material may be doped with one or more suitabledopant species, as may be necessary or desirable for a given end use ofthe bulk M*N material body (subsequent to its separation from thesacrificial substrate on which it is grown, by etch-away of thesacrificial substrate from the M*N material). The doping may be carriedout in any suitable manner during the growth of the M*N material, toyield n-type, p-type or semi-insulating doping. The HVPE processpreferably used to grow the M*N on the sacrificial substrate is highlyamenable to doping.

Doping is carried out by introduction of the gas phase precursor for thedopant to the growth chamber during the growth of the M*N single crystallayer. The dopant in such method is introduced in the vapor phase and isadvantageously controlled by a suitable gas flow controller, e.g., amass flow controller, needle valve in the dopant precursor feed line,etc. The dopant can be delivered in concentrated form or with a suitablediluting carrier gas. The range of dopant flow can be 0.01 sccm to 10slm, for example 0.1-100 sccm. The dopant precursor is desirably stablein a hot-wall environment to prevent deposition on the wall surfaces ofthe system and to ensure transport to the growth surface. Alternatively,the doping may be carried out by ion implantation or other suitabledoping methodology, either in situ or ex situ.

N-type doping of the M*N material during growth may be carried out withdopant species, such as Si, Ge,S, and Se. For p-type doping, suitabledopant species include Mg, Zn and Be. For semi-insulating doping, theforegoing dopants may be used, with species such as V and Fe.Semi-insulating doping preferably is carried out with dopant specieshaving a suitably large activation energy, e.g., an activation energygreater than about 25% of the band gap energy for the material beingdoped.

The dopant flow can be controlled during the growth of the M*N layer toallow co-doping or ramped doping, or any other controlled doping schemeappropriate to the M*N material and its end use. Further, the doping canbe controlled at the initiation of the growth to allow improved backsideohmic contacts to the conductive M*N substrate article produced by theprocess of the invention.

The HVPE process of growth and removal can be carried out at anysuitable pressure level, e.g., atmospheric pressure or subatmosphericpressure. Further, a differential pressure of >0.1 torr isadvantageously maintained between the etching chamber and the growthchamber in a two-chamber system, to minimize cross-contamination.

For example, extremely good results have been achieved in carrying outthe growth process at pressures on the order of 50 torr. In general, itis preferred to carry out the growth process at subatmospheric pressurelevels, e.g., a pressure of 1 millitorr to about 1 atmosphere, morepreferably from about 1 millitorr to 100 torr, and most preferably fromabout 1 to about 1000 millitorr.

FIG. 1 is a perspective view of a bulk single crystal M*N article 10having a generally cylindrical or disc-shaped form, in which the sideface 12 defines a diameter d. A top main surface 16 of this article isin spaced relationship to a corresponding bottom main surface (notshown), to define a thickness z therebetween, as measuredperpendicularly to the plane of the top main surface 16.

This bulk single crystal M*N has three-dimensional character wherein thediameter is at least 100 micrometers (μm) and the z direction is atleast 1 μm. In a preferred aspect, the dimension d is at least 200 μmand the dimension z is at least 100 μm. The bulk single crystal M*Narticle may suitably have a thickness dimension z of at least 100micrometers, and a diameter of at least 2.5 centimeters.

Such article 10 may be utilized as a substrate for the formation ofmicroelectronic structure(s) thereon, e.g., on the top main surface 16thereof. Illustrative microelectronic structure(s) include components orassemblies for devices such as LEDs, lasers, transistors,modulation-doped transistors, with applications in full color displays,high density optical storage systems, excitation sources forspectroscopic analysis applications, etc.

FIG. 2 is a side elevation view of a silicon substrate 20 comprising agenerally disc-like article 22 which is useful as a supporting base fordeposition of single crystal M*N on a top main surface 24 thereof. Thesilicon substrate may be of any suitable type as regards its structureand method of formation. It will be recognized that the substrate itselfmay be of suitable material other than silicon, and in general anyappropriate material may be employed which is useful for the depositionof M*N thereon. In one embodiment, the substrate 20 may be extremelythin, to minimize the number of defects remaining in the M*N grownlayer.

On the top surface 24 of the silicon substrate article 22, M*N isdeposited by any suitable deposition technique, such as thoseillustratively discussed hereinabove. For example, GaN may be depositedby the hydride or chloride techniques. In another embodiment, GaN may bedeposited in a nitrogen atmosphere in a chemical vapor depositionreactor, using a suitable organometallic source reagent for the galliumcomponent of the GaN film or layer to be laid down on top surface 24.

Suitable source reagents for the gallium component of the M*N film orlayer include gallium and gallium alkyl compounds such astrimethylgallium. In general, the gallium source reagent may compriseany suitable precursor compound or complex which undergoes littledecomposition at standard temperature and pressure conditions (25° C.,one atmosphere pressure) and which is suitably decomposable at elevatedtemperature to combine with a suitable nitrogen source to form the GaNlayer. It is understood by those familiar in the field that this shouldbe done without formation of by-products which may contaminate orotherwise preclude the efficacy or utility of the deposited M*N film orlayer, or which may impair the efficiency of such film or layer. It isalso understood by those experienced in the field that other column IIIelements of the Periodic Table may be added or substituted for the Gaprecursor. For example In and Al precursors may be used to form M*Ncompounds.

The deposition of the M*N layer is performed in a modified system madeof conventional crystal growth components as described above.

FIG. 3 is a side elevation view of the silicon substrate 20 of FIG. 2,having a layer of single crystal M*N 26 deposited on the top surface 24of the silicon disc-like article 22, by deposition techniques asdescribed hereinabove.

FIG. 4 is a side elevation view of the silicon/M*N structure of FIG. 3,showing the etching action of a silicon etchant on the silicon substrateportion of the structure. For silicon substrates, hydrogen chloride is agaseous etchant that is etchingly effective at the M*N growthtemperature. If the substrate is some material other than silicon, anetchant that is appropriate for that material must be chosen. Hydrogenchloride also may be used to etch gallium arsenide, but silicon carbideand sapphire may require more aggressive etching treatments. Consistentwith the process requirements as to purity and low particulateconcentrations, the etching process may be assisted by plasma, laserradiation, etc. as may especially be required with the more refractorysubstrates such as silicon carbide or sapphire.

FIG. 5 is a side elevation view of the silicon substrate of FIG. 2,having an intermediate layer of silicon-doped n-type M*N thereon, withan upper layer of single crystal M*N deposited on the top surface of theintermediate layer of silicon-doped n-type M*N.

The methodology of the present invention may be utilized to form galliumnitride articles of very large size, such as 3 inch diameter wafers oreven wafers as large as 18 inches in diameter. The M*N layers depositedon large sacrificial substrates have corresponding dimensions and thusprovide substrate bodies of very large size, as suitable for forming aplurality of microelectronic structures on the surface thereof.

FIG. 6 is a side elevation view of the article of FIG. 5 after removalof the sacrificial substrate portion thereof, yielding a product articlecomprising a layer of single crystal M*N 26 having associated therewithon its bottom surface a layer 30 of silicon-doped n-type M*N.

The article shown in FIG. 6 thus may comprise a layer of galliumnitride, having a thickness of for example of 300 micrometers, with aheavily n-type silicon-doped layer on the bottom. This n-type layer isuseful for making low resistance ohmic contacts to n-type M*N.

It will be recognized that the description of n-type silicon doped M*Non the bottom of the grown M*N layer is intended for illustrativepurposes only, and in practice the dopant may be of suitable materialwhich is epitaxially compatible with the original base or sacrificialsubstrate layer and the M*N layer and advantageous in the processing orproduct structure of the M*N articles of the invention.

Alternatively, an interlayer may be employed between the original baseand sacrificial substrate layer and the layer of M*N to enhance thecrystallinity or other characteristics of the grown M*N layer. Thisso-called buffer layer is commonly used in heteroepitaxial growth toimprove crystal quality. For example, in this case it may comprise agrown layer of silicon on the sacrificial silicon substrate, to improvethe surface of the substrate before deposition of the M*N. The bufferlayer may comprise one or more strained layers such as a superlattice.As a still further alternative, the interlayer may comprise a releaselayer or thin film of a coating or material which assists the removal ofthe M*N layer from the original base or substrate layer. The sacrificialsubstrate may be of extremely thin thickness, not only to facilitate itssubsequent removal by etching, but also to increase the probability thatdefects generated during M*N growth will end up in the sacrificialsubstrate layer.

The sacrificial substrate may optionally be provided with a protectiveintermediate layer deposited thereon prior to growth of the M*N layer,so that the protective layer will prevent decomposition of the singlecrystal substrate while M*N growth is proceeding. The protective layermay be formed by any suitable technique.

The substrate may also utilize an intermediate layer on the sacrificialsubstrate that functions in the etch removal of the sacrificialsubstrate as an etch stop, to prevent etching of the M*N epitaxiallayer. Such intermediate layer should be more resistant to etching atthe growth temperature than either of the sacrificial substrate materialor the bulk growth M*N material, e.g., Si and GaN when Si is thesacrificial substrate material of construction and GaN is the bulkgrowth material on such substrate. For example, AlN and SiC arepotentially useful etch stop layer materials.

Such intermediate layer(s) may be formed in situ during the processingof the sacrificial substrate prior to bulk growth of the M*N materialthereon, or ex situ (prior to introduction to the growth chamber forgrowth of M*N thereon).

FIG. 7 is a schematic depiction of a light emitting diode device 70fabricated on an n-type single crystal GaN substrate 74 according to oneaspect of the invention. In this example, on one surface of thesubstrate 74 an epitaxial n-type GaN layer 73 is grown, followed by ap-type GaN layer 72. An electrical contact 71 is made to the upperp-type GaN layer, and an electrical contact 75 is made to the GaNsubstrate. The contacts may be formed of any suitable material known inthe art, as for example nickel, gold, germanium or indium. Electroncurrent flows in the n to p direction, and light is emitted in the blueto ultraviolet wavelength region as recombination occurs.

FIG. 8 is a schematic depiction of an ohmic contact structure 80fabricated on a single crystal GaN article 81 according to one aspect ofthe invention. Silicon-doped GaN layer 82 is formed by diffusion ofsilicon out of a sacrificial silicon substrate during the growth of thesingle crystal GaN article, as described above. After the siliconsubstrate has been etched away, metal layer 83 is deposited on thesilicon-doped GaN layer. The metal layer may be formed of any suitablecontacting material known in the art, as for example nickel, gold,germanium or indium, which can provide a low-resistance electricalcontact to the GaN substrate via the doped layer.

FIG. 9 is a schematic of a wafer carrier 91 suitable for carrying outthe process of the present invention, showing (a) the sacrificialsubstrate 92 at the start of the M*N growth, (b) a M*N structure 93grown on the sacrificial substrate, and (c) the M*N structure 93 afterremoval of the sacrificial substrate. Such a wafer carrier could, forexample, be used in a two-chambered reactor system where the wafercarrier separates the two chambers. Small tabs on the bottom of thecarrier hold the sacrificial substrate in place, as shown in FIG. 9( a).M*N growth occurs in the top chamber. Growth proceeds bothperpendicularly to as well as parallel to the substrate surface. Afterseveral hundred microns of growth, the M*N will extend over the edge ofthe sacrificial substrate, as shown in FIG. 9( b). This overhang helpsprovide a seal between the two chambers. Sealing is further enhancedduring the growth by keeping the pressures in the two chambersapproximately equal or slightly lower in the deposition chamber tominimize diffusion. Without allowing the temperature to vary more than100° C., and preferably less than 25° C., the etchant species isintroduced into the lower chamber. The sacrificial substrate is etchedaway, leaving the M*N layer sitting in the recess of the carrier asshown in FIG. 9( c). During the etching sequence, cross-diffusion isminimized by keeping the pressure in the upper chamber equal to orslightly higher than the pressure in the lower chamber. Upon completionof etching and cool down, the carrier can then be withdrawn from thereactor to unload the system. It is clear that this type of system canbe scaled up to process many sacrificial substrates simultaneously.

As mentioned above, the M*N bulk crystal material of the inventioncontemplates binary as well as ternary and quaternary III-V nitridecompounds, silicon carbide, and all possible crystal forms, includingall cubic, hexagonal and rhombohedral modifications, and all SiCpolytypes, within the scope hereof. Compositionally graded ternary andquaternary compounds such as AlGaN or AlGaInN are also envisioned, asare M*N materials in which the dopant concentration is varied.

While the invention has been described with regard to specificembodiments, structure and features, it will be recognized that theinvention may be modified or otherwise adapted to a specific end useapplication, and all variations, modifications, and embodiments of theinvention as claimed are to be regarded as being within the spirit andscope of the invention.

1. A method of making a free-standing III-V nitride single crystalarticle, comprising: growing single crystal III-V nitride material, onand across a surface of a heterogeneous substrate having a diameter orcorresponding dimension in an x,y plane of the surface that is at least2.5 centimeters, to a thickness of at least 100 micrometers, by a vapordeposition process conducted at elevated growth temperature; andremoving the heterogeneous substrate from the single crystal III-Vnitride material grown to said thickness, while the single crystal III-Vnitride material is at temperature within 300° C. of said elevatedgrowth temperature and prior to cooling of said single crystal III-Vnitride material to temperature more than 300° C. below said elevatedgrowth temperature, to yield a free-standing III-V nitride singlecrystal article having a diameter or corresponding dimension in an x,yplane that is at least 2.5 centimeters, and is at least 100 micrometersin thickness.
 2. The method of claim 1, wherein the single crystal III-Vnitride material is grown to a thickness that is substantially greaterthan thickness of said heterogeneous substrate.
 3. The method of claim1, wherein said elevated growth temperature comprises temperature in arange of 800 to 1300° C.
 4. The method of claim 1, wherein thefree-standing III-V nitride single crystal article has a diameter orcorresponding dimension in an x,y plane that is greater than 10 inches.5. The method of claim 1, wherein the vapor deposition process isconducted at subatmospheric pressure.
 6. The method of claim 1, whereinthe subatmospheric pressure is in a range of from 1 millitorr to about 1atmosphere.
 7. The method of claim 1, wherein the subatmosphericpressure is in a range of from 1 millitorr to about 100 torr.
 8. Themethod of claim 1, wherein the subatmospheric pressure is in a range offrom 1 millitorr to about 1000 millitorr.
 9. The method of claim 1,further comprising fabricating a microelectronic structure on thefree-standing III-V nitride single crystal article.
 10. The method ofclaim 1, wherein said III-V nitride is gallium nitride.
 11. The methodof claim 10, wherein said free-standing III-V nitride single crystalarticle has a diameter or corresponding dimension in an x,y plane thatis in a range of from 3 inches to 18 inches.
 12. The method of claim 1,wherein the heterogeneous substrate comprises material selected from thegroup consisting of silicon, silicon carbide, gallium arsenide,sapphire, magnesium aluminate, magnesium oxide, scandium aluminummagnesiate, lithium aluminate, lithium gallate, zinc oxide, graphite,glass, metal nitride, and silicon dioxide.
 13. The method of claim 1,wherein the heterogeneous substrate comprises a substrate selected fromthe group consisting of silicon-on-insulator substrates, compliantsubstrates, substrates containing implant species, and twist-bondedsubstrates.
 14. The method of claim 1, wherein the heterogeneoussubstrate is positioned between a growth chamber adapted to carry outsaid growing, and a removal chamber adapted to carry out said removing,and wherein said growing is conducted for sufficient time to grow saidsingle crystal III-V nitride material over edges of the surface of saidheterogeneous substrate to enhance sealing between the growth chamberand the removal chamber.
 15. The method of claim 14, wherein pressure inthe growth chamber is equal to or less than pressure in the removalchamber during said growing.
 16. The method of claim 15, whereinpressure in the growth chamber is equal to or greater than pressure inthe removal chamber during said removing.
 17. The method of claim 1,wherein said removing comprises chemical action on the heterogeneoussubstrate.
 18. The method of claim 17, wherein said chemical actioncomprises use of hydrogen chloride or hydrogen fluoride.
 19. The methodof claim 1, wherein said growing is carried out with diffusion ofspecies from the heterogeneous substrate into the III-V nitride materialfor doping thereof.
 20. The method of claim 19, wherein theheterogeneous substrate comprises silicon, and the III-V nitride singlecrystal article is silicon-doped.
 21. The method of claim 1, wherein theheterogeneous substrate contains implanted hydrogen, and said removingincludes fracturing the substrate from the III-V nitride material by insitu pressure building at elevated temperature in the heterogeneoussubstrate.
 22. The method of claim 21, wherein said fracturing isconducted during said growing of single crystal III-V nitride materialon the heterogeneous substrate.
 23. The method of claim 21, wherein saidfracturing is conducted after said growing of single crystal III-Vnitride material on the heterogeneous substrate.
 24. The method of claim1, further comprising doping of the single crystal III-V nitridematerial during said growing.
 25. The method of claim 24, wherein saiddoping comprises doping with at least one dopant species selected fromthe group consisting of Si, Ge, S, Se, Mg, Zn, Be, V and Fe.
 26. Themethod of claim 1, further comprising fabricating a light emitting diodeon said free-standing III-V nitride single crystal article.
 27. Themethod of claim 14, wherein the heterogeneous substrate is disposed in awafer carrier between the growth chamber and the removal chamber. 28.The method of claim 27, wherein said removing comprises exposure of theheterogeneous substrate to a halogen-containing gas in the removalchamber.
 29. The method of claim 1, wherein the III-V nitride materialcomprises GaN and the heterogeneous substrate comprises sapphire. 30.The method of claim 1, comprising removing the heterogeneous substratefrom the single crystal III-V nitride material grown to said thickness,while the single crystal III-V nitride material is at temperature within100° C. of said elevated growth temperature and prior to cooling of saidsingle crystal III-V nitride material to temperature more than 100° C.below said elevated growth temperature.
 31. The method of claim 1,comprising removing the heterogeneous substrate from the single crystalIII-V nitride material grown to said thickness, while the single crystalIII-V nitride material is at temperature within 50° C. of said elevatedgrowth temperature and prior to cooling of said single crystal III-Vnitride material to temperature more than 50° C. below said elevatedgrowth temperature.
 32. The method of claim 1, comprising removing theheterogeneous substrate from the single crystal III-V nitride materialgrown to said thickness, while the single crystal III-V nitride materialis at temperature within 25° C. of said elevated growth temperature andprior to cooling of said single crystal III-V nitride material totemperature more than 25° C. below said elevated growth temperature. 33.The method of claim 1, wherein said removing comprises use of plasma.34. The method of claim 1, wherein said removing comprises use of laserradiation.